beta-hydroxydialkyl peroxides



Patented July 29, 1952 STATES PATENT OFFICE I Q 7 fl-HYDROXY'lfliZZfiZZl PEROXIDES- I Maurice R. Barusch, Richmond, and. Ja Q! Payne, Concord, Califl, assignors to California Research Corporation, San Francisco,Ca1if., a

corporation of Delaware No Drawing. Application July l 7, 950,

Ser al N 174 357 (Cl. 260:4i10') 10 Claims.

1 This invention relates to new and useful organid pe ox des and .to a method for producing them. More particularly, it relates to fi-hydroxydialkyl peroxides having structures illustrated by the formulae in which R and B may be alkyl 7 or aralkyl groups or hydrogen atoms:

R-oH-omooR' R- on o R CHzOH It has been found that 8-hydroxydialky1 peroxides may be preparedby condensing an epoxyalkane having the oxygen linked to two adjacent carbon atoms with an alkyl hydroperoxide. The reaction occurring in the formation of the o-hydroxydialkyl peroxides may be illustrated as follows:

RCHCH2 ROOH non-011.0011

OH LR-CH-OOR As shown in the above equation two isomeric ,fi-hydroxydialkyl peroxides may be produced during the reaction,. one having the carbinol group arranged in a primary alcohol structure and the other having the carbinol group arranged in a secondary alcohol structure, depending upon which ep'oizide carbon oxygen bond is broken in the reaction. The reaction is facilitated by the employment of catalysts, alkalies and mineral acids being especially effective. When an acid catalysts is employed, both isomers are formed and when a bas'i'c catalyst is employed the isomer having the carbinol group in secondary alcohol structure predominates in the product.

The following examples are provided to illustrate the manner in which the formation of the fi-hydroxydialkyl peroxides of the invention may be prepared. It Should be understood that the specific reactants employed in the examples are illustrative only and not limiting, since the reaction is essentially a reaction between the functional groups of the respective reactants and proceeds almost independently of a specific size or character of the hydrocarbonportion of the molecules of the reactants.

Example 1 lmol of ethylene oxide and cc.cof ethylether were introduced into a 500 cc. round bottom flask fitted with a mercury sealed stirrer, dropping funnel, and a condenser. The flask was imm in an ice bath and the contents were cooled to a temperature below 40 F. 15 milliliters of a 0% lu ion of pota s um h dr de in w e were introduced into thejijaslg. 0.33. mol of tertiary butyl hydrop'eroxide were introduced into the flask drop-wise controlling the rate ofintroduction to maintain the temperature below about 59 F. On completion of the addition, the reaction mixture was allowed to come to room temperature and then was slowly heated to reflux in a hot water bath. The mixture was stirred continuously durin the heating. Heating was continued for approximately 2 hours during which period the caustic layer developed a brown color. Purification was accomplishedby vacuum fractionation. vp-hydi-"oxyethyl tertiary butyl peroxide was formed during the reaction' Example 2 The procedure described in Example 1, omitting only the-introduction ofthe ether, was followed in this example. 0.67 molof 1,2.-propylene oxide were contacted with 0.17 mol of tertiary butyl hydroperoxide inthe presence of 10 cc. of 40% aqueous potassium hydroxide.- fl-hydroxypropyl tertiary butyl peroxide was formed during the reaction.

Example -3 Following the procedure of Example 2, 1,2- isobutylene oxide was reacted with tertiary butyl hydroperoxide. 1 mol of the epoxide and 0.42 mol of the hydroperoxidewere contacted in the presence of 20 cc. of 40% aqueous potassium hydroxide.- fi-hydroxyisobutyl tertiary butyl peroxide was produced during the reaction.

The properties of the B-hydroxydialkyl peroxides produced in the above examples and combustion analytical data are tabulated below.

Calculated Found Rcfrace Den ity B i i Index di Point, F. Per- Perler- P61" N20 cent cent cent cent 0. H C. .H

' B-hydroxyethyltert.butyl peroxide. 1. 1249 0.9561 99at2rnm 53. 71 10. 52 53. 79 10.49 B-hydroxypropyl tert. butyl perox- 1. 4184 9296 99 at 2.5 mm. 56. 73 10.88 57 10. 75

ide. V B-hgdroxyisobutyl tort. butyl pcrox- 1. {i 0. 9985 99 at i n n 59. 23 ll. 11. 23

3 Solid derivatives of the p-hydroxyethyl and the p-hydroxypropyl tertiary butyl peroxides were prepared. In both cases the 3,5-dinitrobenzoate was synthesized for this purpose. Melting points 4 use, presumably by reason of the presence of two functional groups in the molecules. The peroxides of this invention undergo further condensation reactions with epoxides such as ethylene ii ggfif data for these materials are 5 oxide and they may be reacted with hydrogen 7 Calculated Found Melting 2? Per- Per- P'er- Per- Per- Per cent cent cent cent cent cent o. H N o. H N

-h 1 11 1 t.b t 1 a 146 47.56 4. 91 8.53 47.32 4. 99 8.67 0id 6 f ?f?RY f i .z-?ff: 192 49.12 5.30 8.18 49.4 5.2 8.3

It has been ascertained that the reaction of peroxide or with hydroperoxides to prepare novel the invention as illustrated in the above expolyperoxidic materials such as: amples is essentially one in which the oxirane ring of the epoxyalkanereacts with the hydro- OOH peroxide group of the alkyl hydroperoxide. Their reaction may be illustrated as follows: Q

I 2 o OH -(lCOO- Rio-43111001:

O o 4. H o The presence of longer alkyl chains in the hy- RZCLPCEOOR d er id rs to h no a r iable fr53? 013 111: i fie if reactii ii or yi l zis obtain d These polyPerQXldes may themselves be 9 Similarly the length of the alkane chain of as polymerization catalysts or as synthetic interepoxyalkane molecule has little effect upon the g i' course of the reaction. Higher epoxides, such as those of U. s. Patent No. 2,457,328, may be emg, ffig g f 1 ployed in the reaction. Further, the alkyl porg r u tion of the alkyl hydroperoxide and of the epoxyalkane may be substituted by aryl groups at- OH 1381;:ootfizrggfiaafgxfislgtigg 3:110 115, lfaarfifi 4O wllizerein R is a member of the group consisting of directly attached to the hydroperoxide group. 23 gi fg g tiadlcals and i 32 It has been observed that the reaction of the and g 1 1 8 group consls mg 0 y 1,2-epoxides is more rapid and more complete 3 gs the formula than that of epoxides in which the oxygen is linked to adjacent carbon atoms in the central 343F003 portion of the alkane chain; this lower activity CH OH 2 252 2 E2 g? .i perhfaps a: to stelnc wherein R is a member of the group consisting 1 5 t a g 0 emp of alkyl and aralkyl radicals and hydrogen and XVhen the reaction is conducted with the aid of F3 igij fgfigififj j gmup ns1stmg of alkyl ca alysts,-it is preferred to employ alkaline materials such as the alkali metal hydroxides and g g fi of pizoducmgdfl h-ydmxydlalkyl carbonates and the alkaline earth metal hydroxperoxl es W m compnses Pen ensmg an e-poxyides, or mineral acids such as hydrochloric sulalkane havmg oxygen lmked to two afhacent furic, and phosphoric acids to catalyze the reacg fi z g g g zf' 1k 1 tion.. These catalytic materials are preferably e me o pro.uc1ng 5' y F y employed in aqueous solution peroxides which comprises condensing a 1,2- In the conduct of the reaction of this invention g g g an g I hydroijeyoxlde' high temperatures are avoided because of the 6 me 35s 6 ned m c-alm wherem recognized instability of the hydroperoxide the condensation is catalyzed w1th a basic catactants. Ordinarily, temperatures below 100 F. 60 selected the group conslstmg of are employed, but higher temperatures may be kali metal hydroxides, alkah metal carbonates employed where the stability of the particular and alkahne earth metal hyqroxldgs' hydroperoxide usedvis fairly high. The method defined m Wherqm The fi. hydroxydialkyl peroxides of this invem the condensation is catalyzed by a m1neral ac d. tion have a variety of attractive uses. They may 8. The method as defined in claim 5, wherein be employed as diesel fuel additives to effect the condensation is catalyzed with a basic catacetane number improvement. The fi hydroxy lyst selected from the group consisting of alkali dialkyl peroxides produced in the above examples meta} hydroxldes' alkah meital carbonates and were added to diesel fuels in amount sufficient to alkaline earth metal hydroxlfies' constitute 0.3% by weight of the total fuel. The defined m m whgrem Cetane number increases ranging from 5.9 to 6.3 the condengatmn 1s Patalyzed by mmeml acld were obtained by their employment in a 43 cetane Peroxldes having the formula fuel at this concentration. The s-hydroxydialkyl H H Peroxldes y also be employed as polymeriza- RCfiOOOR tion ratalysts and produce novel effects in this OH R" 5 wherein R and R" are members of the group consisting of alkyl and aralkyl radicals and. hydrogen and R. is a member of the group consisting of alkyl and. aralkyl radicals.

MAURICE R. BARUSCH. JACK Q. PAYNE.

REFERENCES CITED The following references are of record in the file of this patent:

v Number 6 UNITED STATES PATENTS Name Date Milas Apr. 26, 1938 Milas Apr. 26, 1938 Milas Oct. 13, 1942 Dickey Dec. '7, 1948 Pezzaglia, Jan. 9, 1951 Ellingboe Aug. '7, 1951 

4. THE METHOD OF PRODUCING B-HYDROXYDIALKYL PEROXIDES WHICH COMPRISES CONDENSING AN EPOXYALKANE HAVING THE OXYGEN LINKED TO TWO ADJACENT CARBON ATOMS WITH AN ALKYL HYDROPEROXIDE.
 10. PEROXIDES HAVING THE FORMULA 